CN103931041B - Secondary cell - Google Patents
Secondary cell Download PDFInfo
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- CN103931041B CN103931041B CN201280055371.9A CN201280055371A CN103931041B CN 103931041 B CN103931041 B CN 103931041B CN 201280055371 A CN201280055371 A CN 201280055371A CN 103931041 B CN103931041 B CN 103931041B
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- additive
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- battery container
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
Secondary cell (1) including: battery container (11); It is housed in the electrode body (13) within battery container; And containing the electrolyte (14) in initial additive full battery container, this secondary cell is provided with the adding device (capsule (3)) that recovery additive adds to electrolyte, and this recovery additive adds for making deterioration state recover according to the deterioration state of the tunicle being formed at electrode body by initial additive.
Description
Technical field
The present invention relates to a kind of secondary cell.
Background technology
In recent years, the electric vehicle such as electric automobile, plug-in hybrid-power automobile is a lot of practical. The battery of the driving being mounted in such electric vehicle uses the lithium rechargeable battery that can charge.
Lithium rechargeable battery is by using, and lithium ion reacts with electrolyte (electrolyte) and forms solid electrolyte interface (SEI) on the surface of electrode. If the formation of this SEI is insufficient, the problem then having electrolyte and electrode excessive response and make the work of secondary cell become instability, if but the formation of SEI exceedingly carries out, then the lithium ion having movement between the positive pole in battery, negative pole reduces and the problem of deterioration of battery.
So far, for solving such problem, it is known that add such as vinylene carbonate (VC) in the electrolytic solution as additive (referring for example to patent documentation 1). In patent documentation 1, by adding VC and forming the tunicle (being denoted as VC tunicle below) formed by VC at electrode surface, suppress excessively to be formed SEI. But, VC tunicle can peel off gradually due to the dilation of electrode body.
Therefore, in the invention described in patent documentation 1, this VC is put into capsule, enabling over time through slowly adding VC in electrolyte, again form the VC tunicle peeled off due to dilation continuously, it is suppressed that the formation of SEI. Its result is to inhibit the deterioration of battery.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-501419 publication (claim 1 etc.)
Summary of the invention
The problem to be solved in the present invention
In patent documentation 1, owing to capsule is slow releasing capsule, process slowly releases VC over time, deterioration can be made to recover, have effective one side under the use state therefore deteriorated in battery process over time.
But, add additive continuously if, with slow releasing capsule, then it is contemplated that additive also can be discharged over time through not deteriorating at battery. There are the following problems in this case: additive excessively discharges, and VC tunicle becomes blocked up thus internal resistance also uprises. Additionally, such problem is not limited to VC, produce too when putting into other additives for making deterioration state recover.
Therefore, it is an object of the invention to solve above-mentioned problem of the prior art, it is provided that a kind of need not excessively add the secondary cell that additive just can suppress the deterioration of battery effectively.
For solving the scheme of problem
The secondary cell of the present invention includes: battery container; It is housed in the electrode body within above-mentioned battery container; And containing the electrolyte in initial additive full above-mentioned battery container, above-mentioned secondary cell is characterised by, being provided with the adding device that recovery additive adds to electrolyte, above-mentioned adding device is for making deterioration state recover according to the deterioration state of the tunicle being formed at above-mentioned electrode body by above-mentioned initial additive. By adding the recovery additive for making deterioration state recover according to deterioration state, it is possible to effectively suppress the deterioration of battery. Additionally, the deterioration state that makes described herein recovers to refer to, the deterioration state that the tunicle formed by additive peels off, from electrode, the battery caused due to dilation is made to recover.
Preferably, the above-mentioned adding device intrinsic pressure rising in the above-mentioned battery container caused because of the deterioration of above-mentioned secondary cell for, more than predetermined value, adding above-mentioned additive to above-mentioned electrolyte. That is, detected the deterioration of battery by intrinsic pressure rising, thus add additives to above-mentioned electrolyte such that it is able to more effectively suppress the deterioration of battery.
As the preferred embodiment of the present invention, the intrinsic pressure change that above-mentioned predetermined value causes can be enumerated out more than dilation during because of the discharge and recharge of above-mentioned electrode body.
Preferably, above-mentioned adding device has the isolated location of above-mentioned additive and above-mentioned electrolyte isolation, intrinsic pressure is deformed according to above-mentioned by this isolated location, thus being discharged to above-mentioned electrolyte by above-mentioned additive. By so not there is mensuration intrinsic pressure determination unit especially and directly by according to intrinsic pressure and that carry out deforming parts are constituted, it is possible to add additive more easily.
Preferably, above-mentioned adding device is to be contained within above-mentioned additive, capsule as above-mentioned isolated location, and is configured to: if above-mentioned intrinsic pressure for more than predetermined value, then the wall of this capsule breaks thus adding above-mentioned additive to above-mentioned electrolyte. If using such adding device, then can add the additive for making deterioration state recover according to deterioration state easily.
Preferably, above-mentioned adding device includes above-mentioned isolated location and storage part, wherein, above-mentioned isolated location is made up of cartridge and moving part, the end side of above-mentioned cartridge is closed, another side is open, above-mentioned moving part is entrenched in the hollow bulb of this cartridge, move to above-mentioned end side in this hollow bulb because of above-mentioned intrinsic pressure rising, above-mentioned storage part and the initial set up position open communication near end side being arranged at the above-mentioned moving part than above-mentioned cartridge, and deposited above-mentioned additive, above-mentioned adding device is configured to: above-mentioned moving part moves because of above-mentioned intrinsic pressure rising, thus adding above-mentioned additive to above-mentioned electrolyte. if using such adding device, then can add the additive for making deterioration state recover according to deterioration state easily.
Preferred above-mentioned adding device is formed with airtrapping portion in the above-mentioned end side of above-mentioned cartridge. By such composition, it is possible to the intrinsic pressure change that dilation when absorbing the discharge and recharge because of above-mentioned electrode body causes.
The effect of invention
Secondary cell according to the present invention can obtain following excellent results: can add additive according to deterioration state, and can effectively suppress the deterioration of battery.
Accompanying drawing explanation
Fig. 1 is the axonometric chart of the secondary cell of embodiment 1.
Fig. 2 is the sectional view of the secondary cell of embodiment 1.
Fig. 3 is the sectional view of the secondary cell of embodiment 2.
Fig. 4 is the schematic diagram of the adding set of embodiment 3.
Fig. 5 is the schematic diagram of the adding set of another embodiment.
Description of reference numerals
1 secondary cell
3,3A capsule
4,5 adding sets (adding device)
5 adding devices
11 housings
12 caps
13 electrode body
14 electrolyte
15 positive terminals
16 negative terminals
17 positive pole curren-collecting parts
18 negative pole curren-collecting parts
41 cylindrical portion
42 major diameter portions
43 openings
44 storage parts
45 additives
46 piston parts
Detailed description of the invention
(embodiment 1)
Use Fig. 1, Fig. 2 that the 1st embodiment of the present invention is described. Fig. 1 indicates that the axonometric chart of the secondary cell of present embodiment, Fig. 2 (1) are the sectional views along A-A ' line of Fig. 1, and Fig. 2 (2) is the sectional view along B-B ' line of Fig. 1.
Secondary cell 1 includes: the housing 11 of approximate rectangular shape; Be arranged in the peristome of housing 11 thus closing the cap 12 of housing 11. As in figure 2 it is shown, contain electrode body 13 in housing 11. It addition, housing 11 is internal is full of electrolyte 14, electrode body 13 is immersed in electrolyte 14. Electrode body 13 is will to be wound across the sandwich that spacer is laminated by positive plate and negative plate and be formed, and stacked direction is horizontal in figure.
Positive terminal 15 and negative terminal 16 it is provided with at cap 12. This positive terminal 15 is connected to positive pole curren-collecting part 17. It addition, be connected to negative pole curren-collecting part 18 on negative terminal 16. Positive pole curren-collecting part 17 and negative pole curren-collecting part 18 are connected with the positive plate of electrode body 13 and negative plate respectively. That is, positive plate, positive pole curren-collecting part 17 and positive terminal 15 are electrically connected to each other. It addition, negative plate, negative pole curren-collecting part 18 and negative terminal 16 are electrically connected to each other.
Positive plate is made up of normally used positive electrode. As normally used positive electrode, for instance can enumerate out can occlusion release the metal-oxide etc. of the metal-oxide of lithium, the such as metal-oxide of layer structure type, the metal-oxide of spinel-type and metallic compound, oxidizing acid salt form. As the metal-oxide of layer structure, lithium nickel based composite oxide, lithium-cobalt composite oxides, ternary compound oxides (LiCo can be enumerated out1/3Ni1/3Mn1/3O2). As lithium nickel based composite oxide, it is preferable that lithium nickelate (LiNiO can be enumerated out2). As lithium-cobalt composite oxides, it is preferable that cobalt acid lithium (LiCoO can be enumerated out2). As the metal-oxide of spinel-type, LiMn2O4 (LiMn can be enumerated out2O4) etc. lithium manganese based composite oxide. As the metal-oxide of oxidizing acid salt form, LiFePO4 (LiFePO can be enumerated out4), lithium manganese phosphate (LiMnPO4), silicon phosphate lithium etc.
Negative plate is made up of normally used negative electrode active material. As negative electrode active material, normally used active substance can be enumerated out, for instance the material with carbon elements etc. such as lithium metal, lithium alloy, metal-oxide, metal sulfide, metal nitride and graphite. As metal-oxide, for instance stannum oxide, silicon oxide etc. can be enumerated out there is the metal-oxide of irreversible capacity. Graphite as one of carbons material, it is possible to be Delanium, it is also possible to be native graphite, in the present embodiment, uses graphite as the active substance of negative pole.
Positive plate and negative plate can also contain binding agent further respectively, for instance Kynoar can be used. Additionally, the electric conductivity such as acetylene black can also be contained in active material layer improves agent, electrolyte (such as lithium salts (supporting electrolyte), ionic-conductive polymer etc.).It addition, when containing ionic-conductive polymer, it is also possible to containing the polymerization initiator for making described polymer polymerizing.
Electrolyte 14 can enumerate out and be dissolved with normally used electrolytical organic electrolyte, this organic electrolyte such as the ethylene carbonate of cyclic carbonate, Allyl carbonate and as the dimethyl carbonate of linear carbonate, Ethyl methyl carbonate, diethyl carbonate mixed solution in be dissolved with the LiPF about 1 molar concentration6. It addition, be added with vinylene carbonate (VC) in this electrolyte 14 as initial additive.
It addition, in the present embodiment, electrolyte 14 is containing capsule 3,3A, and capsule 3,3A have enclosed the recovery additive (below simply referred to as additive) of the tunicle for recovering electrode surface. In the present embodiment, if reach predetermined intrinsic pressure more than, then discharge, from this capsule 3,3A, the additive being enclosed in inside respectively, it is possible to suppress the deterioration of battery.
Capsule 3,3A are constituted by insoluble in electrolytical resin, and are configured to: set respective thickness and make to break when being applied with predetermined pressure. In the present embodiment, the thickness of capsule 3A is thicker than the thickness of capsule 3, is configured and is difficult to break. If owing to secondary cell deteriorates because of use, the then intrinsic pressure rising of housing 11, therefore, by utilizing the intrinsic pressure of this housing 11 make capsule 3,3A break and discharge the additive enclosed, according to deterioration state, the desired amount of additive can be devoted electrolyte, thus suppress deterioration.
Below, this intrinsic pressure relation with deterioration state is illustrated. Secondary cell owing to using, Lithium-ion embeding in carbon electrode time lithium ion react with electrolyte and produce gas, thus on the surface of electrode formation solid electrolyte interface layer (SEI). SEI when the initialization of secondary cell in order to stably discharge and recharge is needs, if but after this still for continuously forming the state of SEI, the lithium ion that then can move between positive pole-negative pole is not enough, it is easy to become the state (deterioration state) that battery capacity reduces. Namely, when defining SEI, the deterioration reducing such secondary cell of the battery capacity caused is reduced easily caused by the lithium ion that can move between positive pole-negative pole because SEI is formed, with this deterioration simultaneously, the intrinsic pressure rising caused because of gas releasing when SEI is formed and the such problem worse of profile variation making battery.
On the other hand, the vinylene carbonate as initial additive (VC) that would commonly be used for suppressing to be formed SEI in secondary cell adds in the electrolytic solution in advance. Thus, forming VC tunicle at electrode surface and suppress the formation of SEI, its result is to suppress the minimizing of battery capacity, suppresses intrinsic pressure rising simultaneously. But, owing to using secondary cell to make electrode expansion, contraction, VC tunicle can peel off from electrode surface. So, the part in this peeling easily forms SEI, as a result of which it is, the lithium ion that sometimes can move between positive pole-negative pole can reduce and make battery capacity reduce. In this case, if excessively adding VC in secondary cell in advance, then VC tunicle can become too thick sometimes, makes internal resistance increase.
Therefore, in present embodiment, in secondary cell 1, it is contained within, as the capsule 3 of adding device, 3A, capsule 3, the 3A deterioration state according to secondary cell 1, namely adding additive according to intrinsic pressure rising at electrolyte 14. Peel off thus the deterioration state easily forming SEI is consistent with making VC tunicle as mentioned above because of use owing to the state of intrinsic pressure rising refers to, therefore if according to intrinsic pressure rising discharges additive, then the tunicle of electrode surface can be made to recover according to deterioration state.
Broken by capsule 3 and discharge additive, VC tunicle (VC tunicle namely can be made to recover) can be again formed in the region that the VC tunicle of electrode surface peels off, the generation of SEI can be suppressed, the capacity that the minimizing of the lithium ion that can move between positive pole-negative pole causes namely can be suppressed to decline the deterioration of such battery. It is additionally, since in the state of deterioration, i.e. the interpolation additive when the VC tunicle of electrode surface has the region of peeling, therefore can also suppress the resistance rising of VC tunicle itself thicker and battery. Such as, dissolve if formed as capsule after the regular hour, then it is contemplated that: less at access times and do not occur deteriorate, also additive can be discharged from capsule, thus, VC tunicle can be thickening, so not being preferred. Therefore, as shown in the embodiment, it is preferable that be configured to when deterioration and can add additive, thus, it is not necessary to excessively add additive just can effectively suppress the deterioration of battery.
Additionally, intrinsic pressure also can because of discharge and recharge time the expansion of electrode, contraction and change, but because of this electrode expansion, shrink the intrinsic pressure change that causes compared with deteriorating the intrinsic pressure change caused little. Therefore, the expansion of electrode when being set greater than the discharge and recharge of described battery by the predetermined intrinsic pressure value broken by capsule 3, shrink the intrinsic pressure variable quantity caused, capsule 3 will not because of discharge and recharge time the expansion of electrode, contraction and break.
By so adding additive, alternatively it is conceivable to intrinsic pressure will not transfer minimizing to, but by again forming VC tunicle, it is possible to suppress intrinsic pressure rising in certain period. This suppresses the deterioration of battery simultaneously. And, if again making the VC tunicle of electrode surface peel off because of electrode dilation repeatedly afterwards, then intrinsic pressure again gradually rise. So, the capsule 3A beyond capsule 3 broken under low internal pressure breaks and discharges additive. So, by the capsule (in the present embodiment contain two thickness different capsules, but be not limited to this) different containing multiple thickness, it is possible to break in predetermined interior pressure respectively and form VC tunicle.
In addition it is also possible to the addition according to additive contains multiple capsule. Namely, it is also possible to contain multiple capsule 3,3A respectively, it is also possible to contain different numbers respectively according to addition. The capsule that more than 3 thickness is different can certainly be contained.
As constitute capsule 3,3A, insoluble in electrolytical resin, it is possible to enumerate the polyolefin such as polyethylene, polypropylene, polystyrene, nylon, polycaprolactone, polyamide, cellulose etc.
In the present embodiment, with the addition of the additive that can again form VC tunicle, but additive is not limited to above-mentioned VC. As additive, as long as the tunicle peeled off because of the dilation of electrode can be recovered as mentioned above, for instance the compound of ethenylidene ethylene carbonate, fluoro-ethylene carbonate, succinic anhydride, lactide, caprolactam, glycol sulfite, propane sultone (PS), propene sultone, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) and derivant and halogen substiuted can be enumerated out. And, as additive, such as can also comprise ethylenediaminetetraacetic acid, tetramethylethylenediamine, pyridine, two pyridines, ethylenebis (diphenylphosphine), butyronitrile, succinonitrile, iodine and ammonium halogenide, for instance hexamethyl disiloxane, hexakis-methoxy basic ring three phosphonitrile, hexamethyl phosphoramide, cyclohexyl benzene, biphenyl, dimethyl pyrrole and derivant thereof.From these additives, select one or more and make it be contained in capsule 3,3A. Initial additive can also use the additive identical with above-mentioned additive.
The total amount of the additive discharged in once adding is about 0.5～1.0 weight % relative to electrolyte content.
Initial additive and recovery additive can be identical material as in the present embodiment, it is also possible to for different materials. Even if initial additive is different from recovery additive, it is possible to by shield electrode and suppress the formation of SEI to suppress the minimizing of the lithium ion that can move between positive pole-negative pole.
(embodiment 2)
In the present embodiment, capsule is replaced to be used as adding device with embodiment 1 except that the adding set 4 shown in Fig. 3.
Adding set 4 is such as arranged on the inner face side of the cap 12 of secondary cell 1, adds additives in electrolyte 14 according to intrinsic pressure change. Adding set 4 has cylindrical portion 41 and major diameter portion 42, and wherein, major diameter portion 42 is arranged on the end side of cylindrical portion 41, and diameter is bigger than the diameter of cylindrical portion 41. Another side of cylindrical portion 41 is open. In cylindrical portion 41, its long side direction is provided with multiple row opening 43. Each opening 43 has been respectively communicated with storage part 44. Storage part 44 is tubular with the end, has deposited additive 45 respectively. It addition, be provided with piston part 46 in cylindrical portion 41, piston part 46 is substantially uniform with the internal diameter of cylindrical portion 41 and is entrenched in inwall. Piston part 46 is such as made up of materials such as rubber. It is mobile that piston part 46 is configured in cylindrical portion 41. Piston part 46 is arranged on another side of cylindrical portion 41 in an initial condition. By making piston part 46 be arranged on another side of cylindrical portion 41 and be fitted together to, in adding set 4, the state downforce that the side, major diameter portion 42 compared with piston part 46 is configured to there being air is identical with external pressure.
In this adding set 4, if it occur that the deterioration of battery, namely intrinsic pressure rising, then piston part 46 is pressed within pushing and slowly moves to end side, i.e. side, major diameter portion 42 on the long side direction of cylindrical portion 41. Then, as shown in Fig. 3 (2), if piston part 46 is moved down, and cross the storage part 44 near open side of cylindrical portion 41, then the additive 45 leaving storage part 44 in is released in electrolyte 14 through opening 43. Therefore, along with the generation of intrinsic pressure rising, piston part 46 is moved in cylindrical portion 41, and thus the additive 45 in each storage part 44 is released in electrolyte 14.
That is, being also configured in the present embodiment, if the deterioration of secondary cell 1, i.e. VC tunicle are removed and intrinsic pressure rising reaches more than predetermined value, then additive 45 is discharged in electrolyte 14. Thus, owing to when becoming the state of peeling when the VC tunicle on electrode, VC is added, therefore, it is possible to again form VC tunicle in the region that the VC tunicle of electrode peels off, it is possible to make secondary cell recover.
In this case, owing to being provided with major diameter portion 42, therefore, it is possible to intrinsic pressure change when absorbing discharge and recharge. That is, even if having intrinsic pressure change during discharge and recharge, it is also possible to pushed laterally by the air comprised in major diameter portion 42, make detection drops. Thus, piston part 46 is to move because deteriorating the intrinsic pressure change that causes, rather than the intrinsic pressure change caused because of common discharge and recharge and move. Additionally, due to this adding set 4 is arranged on the inner face side of cap 12, therefore, it is difficult to it is subject to the impact of the dilation of electrode body 13.Because electrode body 13 is dilation on its stacked direction.
(embodiment 3)
In the present embodiment, with embodiment 2 the difference is that the piston part 46 of the adding set 5 shown in Fig. 4 is pushed to outside by elastomer.
The adding set 5 of present embodiment is the inner face side that be such as arranged on cap 12 same with adding set 4 (with reference to Fig. 3) also, adds an additive in electrolyte according to intrinsic pressure change. Being provided with spring 51 on adding set 5, one end of spring 51 is connected to the spring base 52 being located in major diameter portion 42, and another side is connected to piston part 46. It is arranged on the piston part 46 of entrance of cylindrical portion 41 by spring 51 to outside thruster pressure, but along with the intrinsic pressure increase made because of deterioration in secondary cell 1, the intrinsic pressure elastic force going above spring 51, piston part 46 is moved to inner side. By such structure, it is possible to critically control piston part 46 according to intrinsic pressure further.
That is, being also configured in the present embodiment, if the decline of the capacity of secondary cell 1, i.e. VC tunicle are peeled off and intrinsic pressure rising reaches more than predetermined value, then additive 45 is discharged in electrolyte 14. Thus, owing to when becoming the state of peeling when the VC tunicle on electrode, VC is added, therefore, it is possible to again form VC tunicle in the region that the VC tunicle of electrode peels off, it is possible to make secondary cell 1 recover.
Adding device is not limited to above-mentioned capsule 3,3A and adding set 4,5. Additive 45 can be added according to deterioration state. If being configured to have by the isolated location of additive 45 with electrolyte isolation, and this isolated location is according to described intrinsic pressure and deform, then it is not necessary to arrange determination unit etc. especially, it becomes possible to add effectively easily additive 45 according to intrinsic pressure change.
The shape of adding set 4,5 is not limited to above-mentioned each embodiment. For example, it is also possible to as it is shown in figure 5, be the shape not having major diameter portion. Further, as it is shown in figure 5, the thickness of cylindrical portion 41 is not certain, it is also possible to be configured to its thickness along with going from another side (open sides) to end side (bottom side) and gradually attenuate. In this case, piston part 46 is along with moving to end side, and becomes the form of the inwall being trapped in cylindrical portion 41 further.
In each embodiment, adding device is arranged in electrolyte, but is not limited to this. Such as, as long as intrinsic pressure change can be utilized to push piston part 46, then be just not limited to configuration in the electrolytic solution.
Claims (7)
1. a lithium rechargeable battery, including: battery container; It is housed in the electrode body within described battery container; And containing the electrolyte in initial additive full described battery container, described secondary cell is characterised by,
Being provided with the adding device that recovery additive adds to electrolyte, described adding device makes deterioration state recover for the deterioration state of the tunicle that basis is formed at described electrode body by described initial additive,
Described adding device is in the intrinsic pressure rising caused because of the deterioration of described secondary cell in described battery container and for more than predetermined value, deformed by the intrinsic pressure pushing in described battery container by this adding device, thus the deterioration state according to described secondary cell adds described recovery additive to described electrolyte
Described adding device has the isolated location of described recovery additive and described electrolyte isolation, and described isolated location is by deforming according to intrinsic pressure in described battery container, thus adding described recovery additive to described electrolyte.
2. lithium rechargeable battery as claimed in claim 1, it is characterised in that the intrinsic pressure change that described predetermined value causes more than dilation during because of the discharge and recharge of described electrode body.
3. lithium rechargeable battery as claimed in claim 1 or 2, it is characterised in that
Described predetermined value according to different multiple intrinsic pressure and be set with multiple,
Intrinsic pressure for more than described predetermined value in described battery container of described isolated location, by deforming according to this predetermined value, thus the deterioration state according to described secondary cell adds described recovery additive to described electrolyte.
4. lithium rechargeable battery as claimed in claim 3, it is characterized in that, described adding device be contained within described recovery additive, as the different multiple capsules of the wall thickness of described isolated location, and be configured to: if described intrinsic pressure for more than described predetermined value, then the wall of the capsule of the wall thickness corresponding with described predetermined value among the plurality of capsule breaks thus adding described recovery additive to described electrolyte.
5. a lithium rechargeable battery, including: battery container; It is housed in the electrode body within described battery container; And containing the electrolyte in initial additive full described battery container, described secondary cell is characterised by,
Being provided with the adding device that recovery additive adds to electrolyte, described adding device makes deterioration state recover for the deterioration state of the tunicle that basis is formed at described electrode body by described initial additive,
Described adding device is in the intrinsic pressure rising caused because of the deterioration of described secondary cell in described battery container and for more than predetermined value, by this adding device by the intrinsic pressure pushing in described battery container, thus the deterioration state according to described secondary cell adds described recovery additive to described electrolyte
Described adding device has the isolated location of described recovery additive and described electrolyte isolation, and described isolated location is by moving according to intrinsic pressure in described battery container, thus adding described recovery additive to described electrolyte,
Described predetermined value according to different multiple intrinsic pressure and be set with multiple,
Intrinsic pressure for more than described predetermined value in described battery container of described isolated location, by moving according to this predetermined value, thus the deterioration state according to described secondary cell adds described recovery additive to described electrolyte,
Described adding device includes described isolated location and storage part, wherein, described isolated location is made up of cartridge and moving part, the end side of described cartridge is closed, another side is open, described moving part is entrenched in the hollow bulb of this cartridge, move to described end side in this hollow bulb because of described intrinsic pressure rising, described storage part and the initial set up position open communication near end side being arranged at the described moving part than described cartridge, and deposited described recovery additive, described adding device is configured to: described moving part moves because of described intrinsic pressure rising, thus adding described recovery additive to described electrolyte.
6. lithium rechargeable battery as claimed in claim 5, it is characterised in that
The intrinsic pressure change that described predetermined value causes more than dilation during because of the discharge and recharge of described electrode body.
7. the lithium rechargeable battery as described in claim 5 or 6, it is characterised in that described adding device is formed with airtrapping portion in the described end side of described cartridge.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011246871A JP5800146B2 (en) | 2011-11-10 | 2011-11-10 | Lithium ion secondary battery |
| JP2011-246871 | 2011-11-10 | ||
| PCT/JP2012/078693 WO2013069622A1 (en) | 2011-11-10 | 2012-11-06 | Secondary cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103931041A CN103931041A (en) | 2014-07-16 |
| CN103931041B true CN103931041B (en) | 2016-06-15 |
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ID=48289996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280055371.9A Expired - Fee Related CN103931041B (en) | 2011-11-10 | 2012-11-06 | Secondary cell |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5800146B2 (en) |
| KR (1) | KR101571988B1 (en) |
| CN (1) | CN103931041B (en) |
| WO (1) | WO2013069622A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425844A (en) * | 2013-09-09 | 2015-03-18 | 浙江万向亿能动力电池有限公司 | Method for improving safety of power battery by isolation type inflame-retardant liquid |
| CN103682241A (en) * | 2013-12-17 | 2014-03-26 | 深圳市格瑞普电池有限公司 | Lithium ion battery provided with non-dust cloths |
| WO2015089749A1 (en) * | 2013-12-17 | 2015-06-25 | 深圳市格瑞普电池有限公司 | Lithium-ion battery provided with non-dust cloth |
| CN103811711A (en) * | 2014-02-27 | 2014-05-21 | 深圳市格瑞普电池有限公司 | Lithium ion battery with capsule |
| KR102048359B1 (en) * | 2015-11-24 | 2020-01-08 | 주식회사 엘지화학 | Pouch-typed Battery Case Having Self-Healing Coating Layer and Pouch-typed Battery Cell Having the Same |
| KR102534508B1 (en) * | 2016-01-27 | 2023-05-19 | 에스케이온 주식회사 | Operation Method for Li-Battery and Apparatus thereof |
| KR102264631B1 (en) * | 2017-01-05 | 2021-06-15 | 주식회사 엘지에너지솔루션 | Secondary battery |
| KR102371195B1 (en) * | 2017-04-07 | 2022-03-07 | 삼성에스디아이 주식회사 | Rechargeable Mattery And Rechargeable battery Module Using The Same |
| KR102279000B1 (en) * | 2018-02-23 | 2021-07-20 | 주식회사 엘지에너지솔루션 | Capacity recovering method for secondary battery and capacity recovering device for secondary battery |
| CN109411830A (en) * | 2018-11-02 | 2019-03-01 | 温州玖源锂电池科技发展有限公司 | A kind of Li ion cells unit |
| CN111048832A (en) * | 2019-10-21 | 2020-04-21 | 江西赣锋电池科技有限公司 | Lithium iron phosphate long-life battery electrolyte for energy storage |
| CN112448038B (en) * | 2021-01-29 | 2021-04-16 | 河南工学院 | Lithium battery electrolyte additive, electrolyte and lithium battery |
| CN116711124A (en) * | 2021-08-26 | 2023-09-05 | 宁德时代新能源科技股份有限公司 | Battery cell, battery and electricity utilization device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213703A (en) * | 2005-07-13 | 2008-07-02 | 株式会社Lg化学 | Lithium secondary battery containing capsule for controlled-release of additives |
| CN101471434A (en) * | 2007-12-27 | 2009-07-01 | 比亚迪股份有限公司 | Capsule and battery containing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5147870B2 (en) * | 2010-01-13 | 2013-02-20 | 株式会社日立製作所 | Lithium ion battery and method for regenerating the same |
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2011
- 2011-11-10 JP JP2011246871A patent/JP5800146B2/en not_active Expired - Fee Related
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2012
- 2012-11-06 CN CN201280055371.9A patent/CN103931041B/en not_active Expired - Fee Related
- 2012-11-06 WO PCT/JP2012/078693 patent/WO2013069622A1/en active Application Filing
- 2012-11-06 KR KR1020147015103A patent/KR101571988B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213703A (en) * | 2005-07-13 | 2008-07-02 | 株式会社Lg化学 | Lithium secondary battery containing capsule for controlled-release of additives |
| CN101471434A (en) * | 2007-12-27 | 2009-07-01 | 比亚迪股份有限公司 | Capsule and battery containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5800146B2 (en) | 2015-10-28 |
| KR20140105454A (en) | 2014-09-01 |
| WO2013069622A1 (en) | 2013-05-16 |
| JP2013105544A (en) | 2013-05-30 |
| CN103931041A (en) | 2014-07-16 |
| KR101571988B1 (en) | 2015-11-25 |
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